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Publication numberUS3372201 A
Publication typeGrant
Publication dateMar 5, 1968
Filing dateJun 17, 1966
Priority dateJun 17, 1966
Publication numberUS 3372201 A, US 3372201A, US-A-3372201, US3372201 A, US3372201A
InventorsRobert E Leary, Iii Louis J Nehmsmann, Leslie M Schenck, John M Walts
Original AssigneeGen Aniline & Film Corp
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Alkoxylation of secondary alcohols
US 3372201 A
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Description  (OCR text may contain errors)

United States Patent 3,372 201 ALKOXYLATION. or SECONDARY ALcoaoLs,

Robert E. Leary, Somerville, Louis J. Nehrnsmann ill, Warren, Leslie M. Schen clr, Mountainside, and, John M, Waits, Clark, NHL, assignors' to General Aniline & Film Delaware No Drawing. Filed June 17, 1966, Ser. No. 558,280 Claims; '(;Cl.'260' '6 1 5) This. invention relates to a novelprocess ofproducing secondary alcohol polyalkylene glycol ethers by alkoxylation of, secondary alcohols using an improved catalyst system.

The alkoxylation of secondary alcohols is Well known in the art, for example, the basic reaction may be depicted as:

of secondary alcohols is a rather sensitive reactionand the problem of undersirable side reactions occuring' is by no means a smallone. Secondary alcohols easily form coordination compounds with' boron trifiuoride" which are very unstableand' upon distillation they tend' 'to split oif boron fluoride dihydrate with the formation'of olefins which contribute undesirable color to the reaction product. Moreover, such a dehydration side reaction PfQduces water in the alkoxylation admixture, thereby resulting in undesirable glycolformation. Thus, the need for an improved process which not only results in an"'eifective product, but which also prevents such side reactions has remained constant.

The principal object of this invention is to provide a processfor producing se ndary alcohol polyallgylene glycol others by alkoxylatib ofse'coh'jdary alcohblshsiiig an improved catalyst system. A further o ctt'is' toprbvidesuch a process that eliminates or atleast minimizes undesirable side reactions. An additional object is to provide such a process that will eliminate unde'sirablef'color in the reaction product and also prevent glycol formation. Other objects of this invention will become readilyapparent asfthis specification proceeds.

We have now discovered t hat the allroxylation of secondary alcohols may be greatly improvejcl fairdthe 'aboye Objects e s y attained b h us ut we was using an improved catalyst system. i More particularly, our invention is directed to the alkoxylation of secondary alcohols employing as'a catalyst a bo d a d b ph phat qm lsxl -gJBFs-tria lsi/ p p at Pk S 9 ,Fs"tI ?ry1Pl $Ph ts tomarta- These complexes not only catalyze the reaction, but also eliminate or substantially minimize undesirable side reactions, such as, the dehydration of the secondary alcohol reactantfBy so doingj the -formationof olefi bodies has been eliminated, the polymerization qf whichcdn tributes undesirable color 'toth'e reaction prod iict. ljurthermore, suppression of the dehydration side reaction eliminates Water from being formed in thealkox" ron admixture, thereby minimizing simple andpolyglycol formation. i

Accordingly, any secondary alcohol may be used as the startirig material in the presentihvention. Amhng the orporation, New Year, N.Y., a tem tation or.

st rrs sss d r h ls. at. b ed in process are those alcohols" having from V to 2t) ,7 carbon atoms, among which the following are illustrative;

Z-heptanol 2,7-dimethyl-4-decan0l 3-he'ptanol 2.-butyl-4-octanol Z-hexanol 2,6,8-trimethyl-4-nonanol 2-octanol 3-ethyl-6-undecanol 2-nonanol 2 methyl-7-ethyl 4 undecanol 3-nonanol 3,9-.diethyl-6-undecanol 4-.n0nanol 2-ieicosanol 5-nonanol 3-eicosano'l Z-decanol 4-eic0san0l Z-dodecanol. 5 e'icosanol,

3-dodecanol 6-eicosanol 8-eicosanol' 9Eeicosanol IO-eicosanol 4-dodecanol- 5dodecanol 6-dodecanol 2-octadecan0l. Z-methyl-7-ethyl-4-nonanol Moreover, instead of employin g the individual second ary alcohols one'm'ay employ a mixture ofthe secondary alcoh'ols'having' from'6 to 20 carbon atoms obtaine'dby' the sulfation or a-ol'efins of'fro'rn 6to2 of c ar'bjon atomswith sulfuric acid followedfby hydrolysis "inaccordahc" witl'i the procedure of W. J. Hickinbottom, Reaetion's' offOrganic Compound sj 'l ongman, creeni'a oenipan London 1948, page 14,0; by thefnormal addition'of'hydrobromic'acid in the dark with"antioxidant's to yield the 2-bromides in accordance with the prbcedureiofi Kharasch Potts, Gig; Chem. 2 ,195 (193.7) fol:- lowedby hydrolysis.- i

Alpha-olefins in the carbon range of from C -C C -C5, c, c C C and C CQ' are commerciallyavailable and contain from 81" to 8,6 weightperc'e ntof straight chain u-olefins, from 05 to 2 weight percent oi straight chain internalfolefins, from 13 to'3w eight percent of branched and 'naphthenic olefi'n's, from 2 to weight percent of paraffins and naphthenes and from 1 to 1 weight percent of aromatics, respectively. These a-olefin compositions or blends of the entire range are ideally suited for the conversion into a mixture of secondary alcohols by sulfation and hydrolysis or conversion into 2-bromides followed by hydrolysis and the crude alcohol mixture distilled and employed-"directly iii the etho'xyla tion of the first stagefOiiemay also employ s cond ary alcohols prepared by 'the conventional oxidation of linear parafiins;

An example of the oxidation route is taught by the British patent, Ser. No. 939,534. In this disclosure, there is described a process for the oxidation of nonaromat ic hydrocarbons to compounds containing" ox gen; includ ing alcohols, which comprises reactin'g'am'ofia'romatic 'hy drocarbon with free oxygen or agas 'containirig'fre'e.

oxygen in the presence of a borateester, the *torr'espona: ing alcohol of which is morevolati-leunder the reaction conditions than is the alcohol produced in the oxidation reaction. A comprehensive report discussing thisi'mpor tant synthesis may be found in a paper entitled, fiynthesisof Higher Aliphatic Alcohols Direct Oxidation'of Paraifinic Hydrocarbons, by A/NfB'ashkirov a'ird V. Y. Kamsolkin, and presented at the'jthwor'ld Betroleum Congress held in New York city during'19 59 An earlier disclosureof this art is treated in 11.8. pater'it 1,247,289.

The chlorinjz ltion of par'aflin' hydrocarhorisds discussed in length Asinger, Geiseleran'd Schmiedl, Chemische Berichte 92 30 5-3101 195,9) drol sis at these by drocarbon halides to the corresponding alcohols is disclosed in US. Baterit Z SZZLZSI FA furtherdiseussion of this route is given'by' F. 'Asinger, Che'rhi' und 'Tech nologie der Paralfin Kbhlehwassegstofie,""puhlisherl b'y Patented Mar. 5, 19 68 Aka-demie-Verlag, Berlin, 1959. Addition of l-lBr to olefins followed by hydrolysis to the corresponding secondary alcohol is discussed by Kharasch and Potts, Org. Chem.'2, 195 (1937).

Any alkylene oxide may be used in the instant process, for example, ethylene oxide, propylene oxide, butylene oxide, styrene oxide and the like, as well as an admixture of ethylene oxide and propylene oxide, such as disclosed in copending application Ser. No. 538,971, filed Mar. 31, 1966, the more preferred being the lower alkylene oxides.

.The BF;;/ phosphate complexes, used as the catalyst of the instant invention, may be easily prepared, for example, by bubbling BP through a trialkyl or a triarylphosphate from about to about 30 C. The resultant complexes contain from about 1 percent to about 25 percent BF and are used in catalytic quantities, usually in such amounts as to provide an amount of BF in the range of 0.05% to 2.0% based on the weight of secondary alcohol to promote the alkoxylation of the secondary alcohols. It should also be understood that in addition to using a single complex catalyst one may use a mixture of two or more such catalysts if he so desires.

The temperature at which the instant reaction is carried out is not critical and may vary over a wide range depending upon such conditions as the starting material, desired product, etc., however, the preferred temperature lies in the range of about 30 to about 150 C. The process may be carried out continuously or discontinuously and under atmospheric to super atmospheric pressures.

The molar ratio of alcohol to oxide present in the instant invention is in no way critical and merely depends on the number of ether linkages one desires in the final product, which normally ranges from about 1 to 150. In the present invention it is preferred to utilize a mole to mole ratio of alcohol to oxide from 1 to 15, especially from 1 to 5, so as to produce anywhere from 1 to 5 ether linkages in the final product.

Any BF /organic phosphate ester complex is suitable for use as the catalyst in the present process. Said phosphate complexes are believed to have the formula:

wherein R represents member selected from the group consisting of substituted and unsubstituted alkyl radicals as well as alkyl radicals and monocyclic aryl radicals. Moreover, the R radicals may be the same or different. Among the more preferred complexes are such BFg/phosphates as:

BF trimethylphosphate BF /triethylphosphate BF /tributylphosphate BF /triphcnylphosphate BF ltrioctylphenylphosphate BF /tri-,8-chloroethylphosphate and BF /trilaurylphosphate.

Advantageous results may be obtained using widely varied ratios of Bl /phosphate complexes.

Utility of the secondary alcohol polyalkylene glycol ethers produced by our invention is Well known in the art, for example, they are very valuable nonionic surface active agents, as disclosed in U.S. Patent 2,870,220. They may also be used as intermediates for preparing numerous wetting agents and detergents, such as their sulfate esters.

The following examples are illustrative of the present invention and are not to be regarded as limitative. It is to be understood that all parts, percentages and proportions referred to herein and in the appended claims are by weight unless otherwise indicated.

4+ Example 1 A solution of BF -triethylphosphate complex catalyst (19.5% BF was prepared by bubbling BF gas through the triethylphosphate at 10 to 20 C. The temperature was maintained below 20 C. by external cooling.

5.4 grams of the above catalyst solution prepared above were addeed to 1050 grams (5.1 moles) of a mixture of C C linear secondary alcohols. VPC data showed the mixture to contain about 30% C secondary alcohols, 20% C secondary alcohols, 27% C secondary alcohols, and 23% C secondary alcohols. The mixture was heated to 85 C. and 450 grams (10.2 moles) of ethylene oxide added over 2 /2 hours. Absorption of the ethylene oxide was rapid and external cooling was used to maintain the temperature in the range of 8085 C. When the addition was complete, the reaction mixture was purged with nitrogen to remove any unreacted ethylene oxide and Was made alkaline to litmus paper by the addition of monoethanolamine. The yield of secondary alcohol polyethylene glycol ethers, based quantitatively on the weight of the ethylene oxide added, was 65.7%. The unreacted alcohols, accounting for 31% of the reaction mixture, were removed by fractional distillation. The undesirable glycol content of the residue was found to be 3.3%.

The residue, a mixture of secondary alcohol polyethylene glycol ethers, was converted to the corresponding ammonium sulfate esters by reaction with sulfamic acid in the usual known fashion. Said sulfate esters exhibited very good utility as surface active wetting agents.

Similar results may be obtained when the above process is carried out using other mixed alcohols or separate secondary alcohols, such as dodecanol-Z, dodecanol-El, n-secondary tetradecyl alcohols and the like, in place of the mixture of C to C secondary alcohols used in Example 1. Likewise, similar results may be obtained when such oxides as propylene oxide, butylene oxide and styrene oxide as well as an admixture of ethylene oxide and propylene oxide such as disclosed in copending application, Ser. No. 538,971 filed Mar. 31, 1966, are substituted in place of ethylene oxide. Moreover, the number of ether linkages may be easily increased by increasing the mole ratio of oxide to alcohol.

Example II A control experiment comparable to Example I was run except that only boron trifluoride was used for catalyzing the ethoxylation reaction.

A total of 900 grams (4.35 moles) of the same commercially available C to C secondary alcohols used in Example I containing 0.08% of boron trifiuoride was heated to 80-85 C. and 383 grams (8.7 moles) of ethylene oxide added over a period of 1 hour using external cooling to maintain the temperature in the range of 80 to C. When the addition was complete, the reaction mixture was purged with nitrogen to remove any unreacted ethylene oxide and made alkaline to lit-mus paper by the addition of monoethanol amine. The yield of secondary alcohol polyethylene glycol ethers, based quantitatively on the weight of the ethylene oxide added, was 61.5% and had an undesirable color. The unreacted alcohols, accounting for 32% of the reaction mixture, were removed by fractional distillation. The undesirable glycol content of the residue was found to be 6.5%

The residue, a mixture of secondary alcohol polyethylene glycol ethers, was converted to the corresponding ammonium sulfate esters by reacting with sulfamic acid in the usual known fashion. These sulfate esters did not exhibit as good utility as the surfactants produced in Example I.

Examples I and II aptly demonstrate the superiority of the instant improved process, as well as the unexpected results produced When the catalyst is a boron trifluoride phosphate complex.

The following examples further serve to illustrate the activity of the instant catalyst system.

Example III A solution of BF -triethylphosphate complex catalyst (5% BF was prepared according to the procedure described in Example I.

Operating as in Example I, two ethoxylation runs of the secondary alcohols were carried out at atmospheric pressure, one at 30 to 40 C., and the other at 80 to 90 C. Both reactions took place rapidly and virtually quantitatively in the presence of 2% of the above prepared BF -triethylphosphate catalyst solution (0.1% BF The yield of secondary alcohol polyethylene glycol ethers, based on the weight of the ethylene oxide added, was 69.70% for the run at the lower ethoxylation temperature and 66.71% for the run at the higher ethoxylation temperature. The unreacted alcohols, accounting for 27.03% of the reaction mixture of the first run and 30.07% of the reaction mixture of the second run, were removed by fractional distillation. The undesirable glycol content in the residue was 3.27% for the lower ethoxylation temperature and 3.30% for the higher ethoxylation temperature.

Similar results were obtained when the ethoxylation was carried out at 140150 C. The ethoxylation may also be carried out in the presence of a solution of BF -triethylphosphate (25% BF with like results.

Example IV Example I was repeated except that it was carried out in the presence of a catalytic amount of a 1% solution of BF -triethylphosphate (0.05% B1 The yield of secondary alcohol polyethylene glycol ether, based quantitatively on the weight of the ethylene oxide added, was 69.20%. The unreacted alcohols, accounting for 27.03% of the reaction mixture, were remove-d by fractional distillation and the undesirable glycol content of the residue found to be 2.79%.

Similar results were obtained by substituting various BF /phosphate complexes, such as BF /trimethylphosphate, BF /tributylphosphate, BF /triphenylphosphate, BF /trioctylphenylphosphate and BF /tri-fi-chloroethylphosphate in for the BF /triethylphosphate complex used in Example IV.

Example V Example IV was repeated using a catalytic amount of a 1% solution of BF -trilaurylphosphate (0.5% BF as the catalyst. The yield of secondary alcohol polyethylene glycol ethers, based qantitatively on the weight of the ethylene oxide added, was 69.10%. The unreacted alcohols, accounting for 28.45% of the reaction mixture, were removed by fractional distillation and the undesirable glycol content of the residue was found to be 2.45%.

Example Vl Example IV was repeated except that a catalytic amount of a 1% solution of BF tri-p-nonylphenylphos phate (0.05% BF was used as the catalyst. The yield of secondary alcohol polyethylene glycol ethers, based quantitatively on the weight of the ethylene oxide added, was 68.51%. The unreacted alcohols, accounting for 28.62% of the reaction mixture, were removed by fractional distillation and the undesirable glycol content of the residue was found to be 2.87%.

Example VII As a control, Example IV was repeated except that a catalytic amount of a 1% solution 015 BE, alone was used as the catalyst. The yield of secondary alcohol polyethylene glycol ethers, based quantitatively on the weight of the ethylene oxide added, was 62.0%. The unreacted alcohols, accounting for 30.3% of the reaction mixture, were removed by fractional distillation and the undesirable glycol content of the residue was found to be 7.6%.

Various modifications and variations of this invention will be obvious to a worker skilled in the art and it is understood that such modifications and variations are to be included within the purview of this application and the spirit and scope of the appended claims.

We claim:

1. In a process for producing secondary alcohol polyalkylene glycol ethers, having from 1 to 5 ether linkages, by reacting a secondary alkanol having from 6 to 20 carbon atoms, with an alkylene oxide at a temperature of about 30 to about C. in the presence of a catalytic amount of BF catalyst; the improvement comprising employing as said catalyst a BF /trialkylphosphate complex wherein each alkyl contains about 1 to 12 carbon atoms or a BF /triarylphosphate complex wherein the aryl groups are monocyclic.

2. A process dependent upon claim 1, wherein the catalyst is a BF /triethylphosphate.

3. A process dependent upon claim 1, wherein the secondary alkanol starting material is a mixture of C to C secondary alkanols.

4. A process dependent upon claim 1, wherein the alkylene oxide is ethylene oxide.

5. A process dependent upon claim 1, wherein the BF phosphate catalyst contains from about 1% to about 25% References Cited UNITED STATES PATENTS 2,293,868 8/1942 Toussaint. 2,355,823 8/1944 Schlegel. 2,870,220 1/1959 Carter.

LEON ZITVER, Primary Examiner. H. T MARS, Assistant Examiner.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2293868 *Dec 29, 1939Aug 25, 1942Carbide & Carbon Chem CorpPolymerization products
US2355823 *Dec 5, 1940Aug 15, 1944 Polyglycol ethers of higher second
US2870220 *Aug 11, 1953Jan 20, 1959Union Carbide CorpProduction of nonionic surface active agents
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3513098 *Aug 7, 1967May 19, 1970West Laboratories IncGermicidal nonionic detergent-iodine compositions
US3910878 *Mar 25, 1971Oct 7, 1975Dow Chemical CoLatent oxyalkylation catalysts
US3932531 *Jul 14, 1972Jan 13, 1976Nippon Shokubai Kaguku Kogyo Co., Ltd.Method of manufacturing alkylene oxide adducts of an aliphatic alcohol
US3959389 *Feb 1, 1974May 25, 1976Nippon Shokubai Kagaku Kogyo Co., Ltd.Multistage
US4115457 *Apr 7, 1977Sep 19, 1978Sandoz Ltd.Polyglycol ether derivatives
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US4217390 *Oct 30, 1978Aug 12, 1980Basf Wyandotte CorporationFiber lubricants derived from the oxyalkylation of a glycerol-1,3-dialkylether
US4399313 *Oct 14, 1980Aug 16, 1983Societe Anonyme Dite: L'orealCosmetics for hair or skin
US4474678 *Mar 29, 1982Oct 2, 1984Shell Oil CompanyAlkanol ethoxylate-containing detergent compositions
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US5000960 *Jan 19, 1989Mar 19, 1991Micro-Pak, Inc.Using bifunctional agent to form disulfide bond
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US8039677Apr 30, 2009Oct 18, 2011E.I. Du Pont De Nemours And CompanyFluoroalkylalkoxylates
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Classifications
U.S. Classification568/618, 502/162, 568/622
International ClassificationB01J27/06, B01J31/26
Cooperative ClassificationB01J27/12, B01J31/1845, B01J27/06, B01J31/0258, B01J2231/4288, B01J2231/48, B01J31/26
European ClassificationB01J27/06, B01J31/02E4B2, B01J31/26